EP0130856B1 - Strahlungsempfindliche Silberhalogenidemulsion die substituierte Arylhydrazide enthält - Google Patents

Strahlungsempfindliche Silberhalogenidemulsion die substituierte Arylhydrazide enthält Download PDF

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EP0130856B1
EP0130856B1 EP84400959A EP84400959A EP0130856B1 EP 0130856 B1 EP0130856 B1 EP 0130856B1 EP 84400959 A EP84400959 A EP 84400959A EP 84400959 A EP84400959 A EP 84400959A EP 0130856 B1 EP0130856 B1 EP 0130856B1
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Prior art keywords
silver halide
further characterized
arylhydrazide
photographic
photographic element
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French (fr)
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EP0130856A3 (en
EP0130856A2 (de
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Thomas Carrol Hess
Karl Eugene Wiegers
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
    • G03C1/48546—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent
    • G03C1/48561—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent hydrazine compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/061—Hydrazine compounds

Definitions

  • This invention is directed to silver halide emulsions and photographic elements.
  • the invention is applicable to negative working surface latent image forming silver halide emulsions and to direct positive silver halide emulsions which form internal latent images.
  • Hydrazines find a variety of uses in silver halide photography. They have been used in negative working surface latent image forming silver halide emulsions to increase speed and/or contrast. They have been used in direct positive internal latent image forming emulsions as nucleating agents.
  • the most efficient hydrazines employed in silver halide photographic systems employ a combination of substituents to balance activity and stability.
  • the stability of hydrazines is increased by attaching directly to one of the nitrogen atoms a tertiary carbon atom, such as the carbon atom of an aromatic ring.
  • the art has long recognized that the activity of these stabilized hydrazines can be increased by the direct attachment of an aryl group to the remaining nitrogen atom.
  • the most commonly employed hydrazines are arylhydrazines.
  • the arylhydrazide can be incorporated directly in a photographic element or in a processing solution for the element.
  • a preferred processing solution is disclosed in the following patent:
  • these nucleating agents contain a moiety for promoting adsorption to the silver halide grain surfaces and are therefore preferably incorporated directly within the silver halide emulsion.
  • Unadsorbed nucleating agents such as those disclosed by P-7, for example, can be present in other photographic element layers or in processing solutions, if desired. Unadsorbed nucleating agents incorporated in photographic elements are often ballasted.
  • the arylhydrazide moiety is initially held in an inactive form as a part of the coupler. Only after coupling has occurred is the arylhydrazide available in an active form and then only in an imagewise distribution. This is fundamentally different from the arylhydrazides noted above, such as those of P-1 through P-15, RD-1, and RD-2, wherein the arylhydrazide is uniformly available in an active form.
  • arylhydrazides of prior art are effective, it was desirable to increase the activity of uniformly available arylhydrazides both as nucleating agent in positive-direct emulsions and as speed and/ or contrast increasing agent in negative emulsions. It is the recognition of this invention that the activity of uniformly available arylhydrazides is increased when one of the a and ⁇ nitrogen atoms is sulfinic acid radical substituted: The remaining of these two nitrogen atoms is not substituted and is therefore provided with a hydrogen atom bonded thereto.
  • the term "uniformly available arylhydrazide” is intended to indicate that the arylhydrazide is uniformly available within the composition or layer in which it is contained in an active form at least as early as before the onset of development.
  • the arylhydrazide is uniformly available to enter into reactions with silver halide grain surfaces that reduce the silver ions thereof to silver at least as early as before the onset of development.
  • Normally uniformly available arylhydrazides are in an active form from their initial introduction into a silver halide emulsion or photographic element. For instance, they are never bound to an another addenda, such as a coupler, in such a way as to interfere with their availability.
  • these sulfinic acid radical substitued uniformly available arylhydrazides can show increased speed and/or contrast, depending upon the specific photographic system chosen.
  • these sulfinic acid radical substituted uniformly available arylhydrazides show increased nucleating activity. They can also reduce rereversal of these emulsions.
  • Figures 1 and 2 are plots of density versus exposure.
  • the uniformly available arylhydrazides having a combination of a hydrogen atom and a sulfinic acid radical substituent attached to the a and ⁇ nitrogen atoms exhibit high levels of activity as compared to corresponding uniformly available arylhydrazides having instead pendant hydrogen atoms on both these nitrogen atoms. This is contrary to the typical observation of degradation or even effective elimination of activity when either or both of the a and ⁇ nitrogen atoms of arylhydrazides are fully substituted.
  • the arylhydrazide structure can be represented by the following formula: wherein
  • acyl is defined as the group formed by the removal of a hydroxy moiety directly bonded to a carbonyl moiety of a carboxy group.
  • Acyl can be represented by the following formula: where R 3 is hydrogen, amino, an alkyl or alkoxy substituent, or an aryl substituent.
  • a particularly preferred acyl group is formyl, in which instance R 3 is hydrogen.
  • Specifically preferred alkyl and alkoxy substituents are alkyl and alkoxy (unsubstituted), most preferably those of from about 1 to 8 carbon atoms, optimally 1 to 4 carbon atoms.
  • Specifically preferred aryl substituents are phenyl and naphthyl.
  • aryl is defined as the organic radical formed by the removal of one pendant atom directly bonded to a ring carbon atom of an aromatic nucleus.
  • the aromatic nucleus can be comprised of a carbocylic aromatic ring, such as a separate or fused benzene ring (e.g. a phenyl or naphthyl ring), or a heterocyclic ring of significant aromaticity (e.g. a pyridyl, pyrolyl, furyl, or thiyl ring).
  • the aromatic nucleus can include ring substituents.
  • the aryl group Ar is preferably phenyl or naphthyl.
  • the phenyl or naphthyl group can be unsubstituted or substituted. Either electron donating or electron withdrawing substituents of the aromatic ring are contemplated, with the former being preferred. Highly electron withdrawing substituents, such as cyano, have been observed to reduce activity. Examples of useful substituents include hydroxy, amino, carboxy, alkyl, alkoxy, halo, and haloalkyl. As herein defined cycloalkyl is subsumed within alkyl moieties.
  • the amino substituents include primary, secondary, and tertiary amino groups. Substituents other than ballasting groups, discussed below, typically contain up to about 8 carbon atoms.
  • Substituents other than ballasting groups typically contain up to 8 carbon atoms.
  • the arylhydrazide When the arylhydrazide is to be incorporated in a photographic element, it is preferably substituted to reduce its mobility.
  • the aryl groups Ar and Ar' are convenient sites for introducing substituent moieties for controlling the mobility of the uniformly available arylhydrazides. Either ballasting moieties or groups for promoting adsorption to silver halide grain surfaces can be employed for this purpose. It is generally most convenient to substitute the Ar group with a mobility controlling group.
  • ballasting groups can take conventional forms.
  • the ballasting groups can be similar to those found in common incorporated couplers and other immobile photographic emulsion addenda.
  • the ballast groups typically contain aliphatic and/or aromatic groups that are relatively unreactive, such as alkyl, alkoxy, amido, carbamoyl, oxyamido, carbamoyloxy, carboxy, oxycarbonyl, phenyl, alkylphenyl, phenoxy, alkylphenoxy, and similar groups, with individual ballasts frequently being comprised of combinations of these groups.
  • the ballasting groups generally contain from 8 to about 30 or more carbon atoms. Ballasted uniformly available arylhydrazides are recognized to be useful in promoting high contrast imaging, which suggests that they retain sufficient mobility to stimulate infectious development.
  • a substituent can be incorporated to promote adsorption to silver halide grain surfaces.
  • Adsorption promoting moieties are preferably linked directly to the aromatic ring of Ar (e.g. the phenyl or naphthyl ring) or can be attached through an intermediate divalent linking group.
  • R 4 and R 5 or R 6 in the X position substituents include alkyl, haloalkyl, alkoxyalkyl, phenylalkyl, phenyl, naphthyl, alkylphenyl, cyanophenyl, halophenyl, or alkoxyphenyl having up to about 18 carbon atoms, with R 4 also specifically including hydrogen.
  • ring structures are 4-thiazoline-2-thione, thiazolidine-2-thione, 4-oxazoline-2-thione, oxazolidine-2-thione, 2 - pyrazoline-5-thione, pyrazolidine-5-thione, indoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, isorhodanine, 2-thio-2,4-oxazolidinedione, and thiobarbituric acid, which can, of course, be further substituted.
  • this ring is preferably a ring of the type formed in cyanine dyes - i.e. an azole or azine ring.
  • Sulfinic acid radical substituted uniformly available arylhydrazides useful in the practice of this invention have been previously synthesized by Hantzsch et al and Borsche et al, cited above. The synthesis of additional specific sulfinic acid radical substituted uniformly available arylhydrazides is taught in the Examples.
  • One illustrative method for preparing uniformly available arylhydrazides which are sulfinic acid radical substituted at the a nitrogen atom is the following:
  • Advantages in photogaphic performance can be realized by using the sulfinic acid radical substituted uniformly available arylhydrazides described above so that they are present during development using an aqueous alkaline processing solution in radiation sensitive silver halide emulsions which form latent images either on their surface or internally by the photoelectron reduction of silver ions to silver atoms.
  • the sulfinic acid radical substituted uniformly available arylhydrazides are generally useful with silver halide photographic systems.
  • Such systems and their component features are generally disclosed in Research Disclosure, Vol. 176, December 1978, Item 17643.
  • the sulfinic acid radical substituted uniformly available arylhydrazides can be employed as nucleating agents with any conventional photographic element capable of forming a direct positive image containing, coated on a photographic support, at least one silver halide emulsion layer containing a vehicle and silver halide grains capable of forming an internal latent image upon exposure to actinic radiation.
  • any conventional photographic element capable of forming a direct positive image containing, coated on a photographic support, at least one silver halide emulsion layer containing a vehicle and silver halide grains capable of forming an internal latent image upon exposure to actinic radiation.
  • the terms "internal latent image silver halide grains” and “silver halide grains capable of forming an internal latent image” are employed in the art-recognized sense of designating silver halide grains which produce substantially higher optical densities when coated, imagewise exposed, and developed in an internal developer than when comparably coated, exposed and developed in a surface developer.
  • Preferred internal latent image silver halide grains are those which, when examined according to normal photographic testing techniques, by coating a test portion on a photographic support (e.g. at a coverage of from 3 to 4 grams per square meter), exposing to a light intensity scale (e.g. with a 500-watt tungsten lamp at a distance of 61 cm) for a fixed time (e.g. between 1 x 10- 2 and 1 second) and developing for 5 minutes at 25°C in Kodak Developer DK-50 0 (a surface developer), provide a density of at least 0.5 less than when this testing procedure is repeated, substituting for the surface developer Kodak Developer DK-50 containing 0.5 gram per liter of potassium iodide (an internal developer).
  • a light intensity scale e.g. with a 500-watt tungsten lamp at a distance of 61 cm
  • a fixed time e.g. between 1 x 10- 2 and 1 second
  • Kodak Developer DK-50 0 a surface developer
  • emulsions are the specific subject matter of GB-A-2,110,831. These emulsions are also disclosed in Research Disclosure, Vol. 225, January 1983, Item 22534.
  • the silver halide grains can also be chemically sensitized with reducing agents, such as stannous salts (U.S. Patent 2,487,850, polyamines, such as diethylene triamine (U.S. Patent 2,518,698), polyamines, such as spermine (U.S. Patent 2,521,925), or bis-(I3-aminoethyl)sulfide and its water soluble salts (U.S. Patent 2,521,926).
  • reducing agents such as stannous salts (U.S. Patent 2,487,850, polyamines, such as diethylene triamine (U.S. Patent 2,518,698), polyamines, such as spermine (U.S. Patent 2,521,925), or bis-(I3-aminoethyl)sulfide and its water soluble salts (U.S. Patent 2,521,926).
  • a simple exposure and development process can be used to form a direct positive image.
  • a photographic element comprising at least one layer of a silver halide emulsion as described above can be imagewise exposed to light and then developed in a silver halide surface developer.
  • Typical silver halide developing agents which can be used in the developing compositions include hydroquinones, catechols, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and color developing agents, that is, primary aromatic amine developing agents, such as, aminophenols and para-phenylenediamines.
  • the color developing agents are preferably employed in combination with black-and-white developing agents capable of acting as electron transfer agents.
  • Illustrative of useful surface developers are those disclosed in U.S. Patents 2,563,785, 3,761,276, 2,456,953, and 3,511,662.
  • the developing compositions can contain certain antifoggants and development restrainers, or, optionally, they can be incorporated in layers of the photographic element.
  • certain antifoggants and development restrainers or, optionally, they can be incorporated in layers of the photographic element.
  • improved results can be obtained when the direct positive emulsions are processed in the presence of certain antifoggants, as disclosed in U.S. Patents 2,497,917, 2,704,721, 3,265,498, and 3,925,086.
  • the sulfinic acid radical substituted arylhydrazide nucleating agents of the present invention can be employed alone or in combination with conventional nucleating agents, such as those of the quaternary ammonium salt, hydrazine, hydrazide, and hydrazone type.
  • conventional nucleating agents such as those of the quaternary ammonium salt, hydrazine, hydrazide, and hydrazone type.
  • conventional nucleating agents are also illustrated by U.S. Patents 4,115,122, 3,719,494, 3,734,738, 4,306,016, 4,306,017, and 4,315,986.
  • the sulfinic acid radical substituted arylhydrazide nucleating agents into the silver halide emulsions in concentrations of from 10- 5 to 10- 2 mole per mole of silver halide.
  • an efficient adsorption promoting moiety is incorporated in the sulfinic acid radical substituted uniformly available arylhydrazide nucleating agent, such as indicated by formula VI, it is generally unnecessary to provide nucleating concentrations in excess of about 10- 3 mole per mole of silver halide.
  • the silver halide emulsions can be spectrally sensitized with cyanine, merocyanine, and other polymethine dyes and supersensitizing combinations thereof well known in the art.
  • Spectral sensitizers in conventional surface sensitive emulsions are comparably effective in the emulsions of this invention. In general, they enhance nucleation.
  • Nonionic, zwitterionic and anionic spectral sensitizers are preferred. Particularly effective are carboxy substituted merocyanine dyes of the thiohydantoin type described by U.S. Patent 2,490,758.
  • the layer units each contain in the emulsion layers or in adjacent hydrophilic colloid layers at least one image dye providing compound. Such compounds can be selected from among those described above. Incorporated dye forming couplers and redox dye releasers constitute exemplary preferred image dye providing compounds.
  • the blue, green and red responsive layer units preferably contain yellow, magenta and cyan image dye providing compounds, respectively.
  • the sulfinic acid radical substituted uniformly available arylhydrazides can be employed alone or in combination with other uniformly available arylhydrazides and hydrazines known to increase contrast over that attainable in the absence of such addenda, such as those disclosed in patents P-1 through P-6, cited above.
  • the sulfinic acid radical substituted uniformly available arylhydrazides allow higher speeds to be realized as compared to conventional arylhydrazides. Concentrations in the photographic elements of at least 10- 4 mole per mole of silver are contemplated in the absence of adsorption promoting moieties.
  • the arylhydrazide compounds are employed in combination with negative working photographic emulsions comprised of radiation sensitive silver halide grains capable of forming a surface latent image and a vehicle.
  • the silver halide emulsions include the high chloride emulsions conventionally employed in forming lith photographic elements as well as silver bromide and silver bromoiodide emulsions, which are recognized in the art to be capable of attaining higher photographic speeds.
  • the iodide content of the silver halide emulsions is less than about 10 mole percent silver iodide, based on total silver halide.
  • the emulsion when the sensitivity resulting from surface development (A), described below, is greater than that resulting from internal development (B), described below, the emulsion being previously light exposed for a period of from 1 to 0.1 second, the emulsion is of a type which is "capable of forming a surface latent image" or, more succinctly, it is a surface latent image emulsion.
  • the sensitivity is defined by the following equation: in which S represents the sensitivity and Eh represents the quantity of exposure necessary to obtain a mean density - - i.e., 1/2 (D-max + D-min).
  • the emulsion is processed at about 20°C for 10 minutes in a bleaching solution containing 3 g of potassium ferricyanide per liter and 0.0125 g of phenosafranine per liter and washed with water for 10 minutes and developed at 20°C for 10 minutes in a developer solution having the following composition:
  • Silver halide emulsions contain in addition to silver halide grains a vehicle.
  • the proportion of vehicle can be widely varied, but typically is within the range of from 20 to 250 grams per mole of silver halide. Excessive vehicle can have the effect of reducing maximum density and consequently also reducing contrast. Thus for contrast values of 10 or more it is preferred that the vehicle be present in a concentration of 250 grams per mole of silver halide or less.
  • the specific vehicle materials are conventional, can be present in other photographic element layers, and correspond to those discussed above in connection with direct positive imaging.
  • Emulsions according to this invention having silver halide grains of any conventional geometric form can be prepared as disclosed in Research Disclosure, Item 17643, cited above, Section I.
  • Sensitizing compounds such as compounds of copper, thallium, cadmium, rhodium, tungsten, thorium, iridium and mixtures thereof, can be present during precipitation of the silver halide emulsion, as illustrated by U.S. Patents 1,195,432; 1,951,933; 2,448,060; 2,628,167; 2,950,972; 3,488,709 and 3,737,313.
  • the emulsions employed need not be chemically sensitized.
  • Sensitization with one or more middle chalcogens, sulfur, selenium, and/or tellurium is a preferred surface chemical sensitization.
  • Such sensitization can be achieved by the use of active gelatin or by the addition of middle chalcogen sensitizers, such as disclosed by Research Disclosure, Item 17643, cited above, Section III. Reduction and other conventional chemical sensitization techniques disclosed therein which do not unacceptably reduce contrast can also be employed.
  • Spectral sensitization of the high contrast silver halide emulsions is not required, but can be undertaken using conventional spectral sensitizers, singly or in combination, as illustrated by Research Disclosure, Item 17643, cited above Section IV. For black-and-white imaging orthochromatic and panchromatic sensitizations are frequently preferred.
  • alkali sulfites e.g., sodium or potassium sulfite, bisulfite or metasulfite
  • Any preservative or preservative concentration conventional in lower contrast processing can be employed, such as, for instance, a sulfite ion concentration in the range of from about 0.15 to 1.2 mole per liter of developer.
  • the developers are typically aqueous solutions, although organic solvents, such as diethylene glycol, can also be included to facilitate the solvency of organic components.
  • the developers contain one or a combination of conventional developing agents, such as polyhydroxybenzene, aminophenol, para- phenylenediamine, ascorbic acid, pyrazolidone, pyarazolone, pyrimidine, dithionite, hydroxylamine or other conventional developing agents. It is preferred to employ hydroquinone and 3-pyrazolidone developing agents in combination.
  • the pH of the developers can be adjusted with alkali metal hydroxides and carbonates, borax and other basic salts. To reduce gelatin swelling during development, compounds such as sodium sulfate can be incorporated into the developer.
  • a specifically preferred adsorption promoting moiety is that described by formula VI.
  • the sulfinic acid radical substituted arylhydrazide is incorporated directly in the silver halide emulsion, rather than being in a separate layer of the photographic element.
  • the arylhydrazide is incorporated in a concentration of less than 10- 2 mole per mole of silver.
  • concentrations of at least 10- 7 mole per silver mole are specifically contemplated, with a range of from 10- 6 to 10- 4 mole per mole of silver being preferred.
  • gold sensitization of the emulsions can be undertaken by conventional techniques.
  • gold sensitization can be undertaken as taught by U.S. Patent 2,642,361.
  • middle chalcogen sensitization i.e., sulfur, selenium, and/or tellurium
  • Conventional chemical sensitizations of these types as well as noble metal sensitizations generally are illustrated by Research Disclosure, Item 17643, cited above, Section III.
  • sulfur and gold sensitized silver bromoiodide emulsions such as taught by U.S. Patent 3,320,069.
  • Exposure and processing of the photographic elements can be identical to that previously described in connection with direct positive and high contrast imaging, although this is not essential.
  • the same pH ranges as described above are generally preferred for processing the increased speed photographic elements.
  • Example 4 differs from the Control Coating of Example 3 in containing 3.8 x 10- 6 moles/mole Ag of the tosylated hydrazide, SA-4, 1-formyl-2-(4-methylphenylsulfonyl)-2-[4-(3-phenylureido)phenyl]hydrazine. The results are listed in Table II.
  • a 0.20 to 0.25 pm grain cubic silver bromoiodide emulsion (97.5/1.5) containing the compound C-6, 1-formyl-2-[4-(3-hexylureido)phenyl]hydrazine, at 2.15 mmoles/mole AG was coated at 4.30 g Ag/m 2 and 2.64 g gel/m 2 on a film support: (C-6)
  • This coating was like the Control Coating, but also contained SA-3 at 0.198 mmole/moleAg.
  • SA-3 0.198 mmole/moleAg.
  • Example 15 The control emulsion described in Example 15 was coated on a film support at 5.81 g Ag/m 2 and 9.69 g gel/m 2 with a gelatin overcoat layer (1.07 g/m 2 ), The coating also contained SA-3 at 0.13 mmole/mole Ag. Samples of this coating were exposed (1/100 s, EG&G sensitometer, Wratten 47B filter) through a graduated step wedge and processed (4 min at 21.1°C) in a N-methyl-p-aminophenol hemisulfate- hydroquinone developer at differing pH. The results are shown below in Table VIII.

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Claims (24)

1. Strahlungsempfindliche Silberhalogenidemulsion mit einem Gehalt an einem gleichförmig zugänglichen Arylhydrazid mit einer Acylgruppe, die über einen Hydrazorest an ein Ringkohlenstoffatomen einer Arylgruppe gebunden ist, dadurch gekennzeichnet, daß ein Stickstoffatom des Hydrazorestes durch einen Sulfinsäurerest substituiert ist.
2. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß der Hydrazorest der folgenden Formel entspricht:
Figure imgb0042
in der bedeuten:
R' Wasserstoff oder einen Sulfinsäurerest-Substituenten und
R2 einen Sulfinsäurerest-Substituenten, wenn R' für Wasserstoff steht und Wasserstoff, wenn R' für einen Sulfinsäurest-Substituenten steht.
3. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 2, dadurch gekennzeichnet, daß sie ein latentes Oberflächenbild erzeugende Silberhalogenidkörner enthält.
4. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 2, dadurch gekennzeichnet, daß sie ein latentes Innenbild erzeugende Silberhalogenidkörner enthält.
5. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß das Arylhydrazid in einer Kozentration von bis zu 10-2 Molen pro Mol Silber vorhanden ist.
6. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß der Sulfinsäurerest-Substituent der folgenden Formel entspricht:
Figure imgb0043
in der Ar für eine Arylgruppe steht.
7. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 6, dadurch gekennzeichnet, daß die Arylgruppe aus einem carbocylischen aromatischen Ring besteht.
8. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 7, dadurch gekennzeichnet, daß die Arylgruppe aus einem Phenylsubstituenten besteht.
9. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 8, dadurch gekennzeichnet, daß der Phenylsubstituent Alkyl-substituiert ist.
10. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß das Arylhydrazid einen Rest für die Förderung der Adsorption an den Oberflächen der Silberhalogenidkörner aufweist.
11. Strahlungsempfindliche Silberhalogenidemulsion nach Anspruch 1, dadurch gekennzeichnet, daß das Arylhydrazid de folgenden Formel entspricht:
Figure imgb0044
in der bedeuten:
Acyl eine Acylgruppe;
Ar eine Arylgruppe;
R' Wasserstoff und
R2 einen Sulfinsäurerest-Substituenten.
12. Photographisches Element mit einer strahlungsempfindlichen Silberhalogenidemulsion, dadurch gekennzeichnet, daß es eine Silberhalogenidemulsion nach einem der Ansprüche 1 bis 11 aufweist.
13. Photographisches Element nach Anspruch 12, dadurch gekennzeichnet, daß es ein direkt-positives Bild zu erzeugen vermag und einen Träger aufweist und daß die Emulsion auf diesem Träger aufgetragen ist und aufgebaut ist aus einem Dispersionsmedium, ein latentes Innenbild liefernden .Silberhalogenidkörnern und pro Mol Silber bis zu 10-2 Mole gleichförmig zugänglichem Arylhydrazid, das als keimbildendes Mittel zu wirken imstande ist und nicht exponierte Silberhalogenidkörner in einem Oberflächenentwickler selektiv entwickelbar machen kann.
14. Photographisches Element nach Anspruch 13, dadurch gekennzeichnet, daß das Arylhvdrazid einen die Adsorption fördernden Thioamidrest aufweist und von der Oberfläche der Silberhalogenidkörner in einer Konzentration von 10-5 bis 10-3 Molen pro Mol Silber adsorbiert ist.
15. Photographisches Element nach Anspruch 14, dadurch gekennzeichnet, daß der Arylrest des Arylhydrazides einen die Adsorption fördernden Rest der Formel:
Figure imgb0045
aufweist, in dem bedeuten:
einer der Reste X und X' steht für ―N(R5)― und der andere der Reste für ―O―,―S― oder ―N(R6)―;
R4 Wasserstoff, einen aliphatischen Rest, einen aromatischen Rest oder gemeinsam mit X oder X' einen heterocyclischen Ring;
R5 und R6 in der X-Position Wasserstoff, einen aliphatischen Rest oder einen aromatischen Rest und
R5 und R6 in der X'-Position Wasserstoff oder einen Benzyl-Substituenten;
wobei gilt, daß mindestens einer der Reste R4, R5, und R6, sofern jeder vorhanden ist, für Wasserstoff steht.
16. Photographisches Element nach Anspruch 13, dadurch gekennzeichnet, daß es einen Teil einer Bildübertragungsfilmeinheit bildet, das zusätzlich enthält:
ein ein Farbbild lieferndes Material, das in Abhängigkeit von der Silberhalogenidentwicklung zwischen einer mobilen und einer immobilen Form zu wechseln vermag und
eine Bildempfangsschicht für die Erzeugung eines sichtbaren übertragenen Farbstoffbildes nach Exponierung und Entwicklung der Emulsionsschicht.
17. Photographisches Element nach Anspruch 12, dadurch gekennzeichnet, daß die Silberhalogenidemulsionsschicht eine negativ arbeitende Schicht ist und ein hoch-kontrastreiches Silberbild zu erzeugen vermag als Folge davon, daß sie ein Dispersionsmedium und strahlungsempfindliche Silberhalogenidkörner mit einem mittleren Durchmesser von 0,7 µm oder weniger aufweist, die ein latentes Oberflächenbild zu erzeugen vermögen und davon, daß in der Emulsionsschicht oder einer benachbarten hydrophilen Kolloidschicht ein gleichförmig zugängliches Arylhydrazid in einer Konzentration von 10-4 bis 10-2 Molen Pro Mol Silber vorliegt.
18. Photographisches Element nach Anspruch 17, dadurch gekennzeichnet, daß das Dispersionsmedium in einer Konzentration von 250 g oder weniger pro Mol Silber vorliegt.
19. Photographisches Element nach Anspruch 17, dadurch gekennzeichnet, daß das Element eine Schleier vermindernde und Kontrast steigernde Menge eines Benzotriazols enthält.
20. Photographisches Element nach Anspruch 12, dadurch gekennzeichnet, daß die Silberhalogenidemulsionsschicht negativ arbeitend und zu einer erhöhten photographischen Empfindlichkeit befähigt ist, als Folge davon, daß sie ein Dispersionsmedium, ein latentes Oberflächenbild erzeugende Silberhalogenidkörner und von den Oberflächen der Silberhalogenidkörner adsorbiert 10-0 bis 10-2 Mole des Arylhydrazides mit einem die Adsorption fördernden Thioamidrest als Substituent der Arylgruppe pro Mol Silber aufweist.
21. Negativ arbeitendes photographisches Silberhalogenidelement nach Anspruch 20, dadurch gekennzeichnet, daß die Silberhalogenidkörner Gold-sensibilisiert sind.
22. Negativ arbeitendes photographisches Silberhalogenidelement nach Anspruch 21, dadurch gekennzeichnet, daß es zusätzlich Schwefel-sensibilisiert ist.
23. Negativ arbeitendes photographisches Silberhalogenidelement nach Anspruch 20, dadurch gekennzeichnet, daß das Arylhydrazid in einer Konzentration von 10-6 bis 10-4 Molen pro Mol Silber vorliegt.
24. Negativ arbeitendes photographisches Silberhalogenidelement nach Anspruch 20, dadurch gekennzeichnet, daß das Arylhydrazid der folgenden Formel:
Figure imgb0046
entspricht, in der bedeuten:
Acyl eine Acylgruppe;
D einen Phenylenrest;
R' Wasserstoff oder einen Sulfinsäurerest-Substituenten;
R2 einen Sulfinsäurerest-Substituenten, wenn R' für Wasserstoff steht und Wasserstoff, wenn R' für einen Sulfinsäurerest-Substituenten steht;
X gleich -0-, ―S― oder ―N(R6)― und
R4 und R6 Wasserstoff, Alkyl, Haloalkyl, Alkoxyalkyl, Phenylalkyl, Phenyl, Naphthyl, Alkylphenyl, Cyanophenyl, Halophenyl oder Alkoxyphenyl, wobei gilt, daß jeder Alkylrest bis zu 18 C-Atome aufweist und wobei ferner gilt, daß nicht mehr als einer der Reste R4 und R6 für Wasserstoff steht.
EP84400959A 1983-05-11 1984-05-11 Strahlungsempfindliche Silberhalogenidemulsion die substituierte Arylhydrazide enthält Expired EP0130856B1 (de)

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US06/493,480 US4478928A (en) 1983-05-11 1983-05-11 Application of activated arylhydrazides to silver halide photography
US493480 1983-05-11

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JPS59212828A (ja) 1984-12-01
US4478928A (en) 1984-10-23
DE3465149D1 (en) 1987-09-03
CA1269877A (en) 1990-06-05
EP0130856A2 (de) 1985-01-09

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